CN112442272A

CN112442272A - Maleimide resin film and composition for maleimide resin film

Info

Publication number: CN112442272A
Application number: CN202010908139.1A
Authority: CN
Inventors: 井口洋之; 堤吉弘; 柏木努
Original assignee: Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd
Priority date: 2019-09-03
Filing date: 2020-09-02
Publication date: 2021-03-05
Anticipated expiration: 2040-09-02
Also published as: TW202111003A; US20210061955A1; JP7115445B2; JP2021038318A; US20220267526A1; CN112442272B; KR20210028120A

Abstract

The present invention addresses the problem of providing a maleimide resin film which is highly filled with inorganic particles and has excellent adhesion. The maleimide resin film comprises: (a) a maleimide represented by the following formula (1) (in the formula (1), A independently represents a tetravalent organic group having a cyclic structure, B independently represents an aliphatic ring having one or more carbon atoms of 5 or more, and an alkylene group having 6 or more carbon atoms optionally containing a heteroatom, Q independently represents an arylene group having 6 or more carbon atoms optionally containing a heteroatom, W represents a group represented by B or Q, n is 0 to 100, and m represents a number of 0 to 100, wherein at least one of n and m is a positive number); (b) (meth) acrylic acid esters; (c) inorganic particles; and (d) a curing catalyst.

Description

Maleimide resin film and composition for maleimide resin film

Technical Field

The present invention relates to a maleimide resin film and a composition for a maleimide resin film.

Background

In recent years, in electronic devices, high-density packaging of semiconductor packages, high integration and high speed of LSIs, and the like have been carried out with the progress of high performance, miniaturization, weight reduction, and the like. With these changes, since the amount of heat generated in various electronic components increases, a countermeasure against heat that effectively dissipates heat from the electronic components to the outside has become a very important issue. As such a thermal countermeasure, a thermally conductive molded body made of a heat dissipating material such as metal, ceramic, or polymer composition is applied to a heat dissipating member such as a printed wiring board, a semiconductor package, a case, a heat pipe, a heat dissipating plate, or a heat diffusing plate. In particular, the number of electronic devices mounted is increased due to safety control such as EV, automatic driving, and collision prevention of an automobile, and crisis control, and heat countermeasure for dissipating heat from light, thin, short, and small electronic devices is important.

Conventionally, high heat conductive resins or molded bodies have been produced by highly filling high heat conductive particles in curable resins such as silicone resins and epoxy resins, but if the high heat conductive particles are highly filled in silicone resins and epoxy resins, the molded bodies become hard and brittle (patent documents 1 and 2).

As a countermeasure, a method of orienting heat conductive particles in a scale-like, fibrous, or plate-like shape in the thickness direction to improve the heat conductivity is known (patent documents 3 and 4). However, this method has a disadvantage of poor productivity because it is difficult to orient the thermally conductive particles in the composition.

A method of improving the thermal conductivity of the composition by improving the thermal conductivity of the resin itself is also known (patent document 5). However, this method is limited to resins such as liquid crystal polymers having a mesogen skeleton, and thus it is difficult to impart flexibility to the cured molded article.

It is also known that a maleimide resin has flexibility and heat resistance due to a main chain skeleton, and is used for a flexible printed wiring board or the like (patent document 6). Further, there is a method of mixing a maleimide resin with an epoxy resin, a phenol resin, or the like, and then highly filling inorganic particles to reduce the linear expansion coefficient. However, this method has insufficient adhesion to electronic components (patent document 7).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2000-204259

Patent document 2: japanese laid-open patent publication No. 2018-087299

Patent document 3: international publication WO2018/030430

Patent document 4: international publication WO2017/179318

Patent document 5: international publication WO2017/111115

Patent document 6: international publication WO2016/114287

Patent document 7: japanese patent laid-open publication No. 2018-083893

Disclosure of Invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to provide a maleimide resin film having a sufficient adhesive force and highly filled with inorganic particles.

Means for solving the problems

The present inventors have conducted extensive studies in order to achieve the above object and, as a result, have found that the above problems can be solved by the following maleimide resin film, thereby completing the present invention.

That is, the present invention provides the following maleimide resin film.

＜1＞

A maleimide resin film comprising:

(a) a maleimide represented by the following formula (1),

(in the formula (1), A independently represents a tetravalent organic group containing a cyclic structure, B independently represents an alkylene group having at least one aliphatic ring having at least 5 carbon atoms and optionally containing a heteroatom and having at least 6 carbon atoms, Q independently represents an arylene group having at least 6 carbon atoms and optionally containing a heteroatom, W represents a group represented by B or Q, n is 0 to 100, and m represents a number of 0 to 100, wherein at least one of n and m is a positive number.);

(b) a (meth) acrylate having 10 or more carbon atoms;

(c) inorganic particles; and

(d) a curing catalyst is used for curing the epoxy resin,

wherein the inorganic particles of the component (c) account for 70 to 90 vol% of the entire resin film.

＜2＞

The maleimide resin film of < 1 > wherein the organic group represented by A in formula (1) is any of tetravalent organic groups represented by the following structural formula,

(the bonding position of the unbonded substituent in the above structural formula is bonded to the carbonyl carbon forming the cyclic imide structure in formula (1)).

＜3＞

The maleimide resin film according to < 1 > or < 2 >, wherein,

(b) the (meth) acrylate having 10 or more carbon atoms as the component (A) has 1 or more aliphatic rings having 5 or more carbon atoms.

＜4＞

The maleimide resin film according to any one of < 1 > - < 3 >, wherein,

(c) the inorganic particles of the component (a) are at least one selected from the group consisting of conductive particles, heat conductive particles, fluorescent materials, magnetic particles, white particles, hollow particles and electromagnetic wave absorbing particles.

＜5＞

The maleimide resin film according to any one of < 1 > - < 4 >, wherein,

(c) the inorganic particles of the component (a) are at least one conductive particle selected from a simple metal substance of gold, silver, copper, palladium, aluminum, nickel, iron, titanium, manganese, zinc, tungsten, platinum, lead or tin, or an alloy of solder, steel or stainless steel.

＜6＞

The maleimide resin film according to any one of < 1 > - < 4 >, wherein,

(c) the inorganic particles of the component (a) are at least one thermally conductive particle selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, beryllium oxide, magnesium oxide, zinc oxide, aluminum oxide, silicon carbide, diamond, and graphene.

＜7＞

The maleimide resin film according to any one of < 1 > - < 4 >, wherein,

(c) the inorganic particles of the component (A) are selected from iron, cobalt, nickel, stainless steel, Fe-Cr-Al-Si alloy, Fe-Si-Al alloy, Fe-Ni alloy, Fe-Cu-Si alloy, Fe-Si-B (-Cu-Nb) alloy, Fe-Si-Cr-Ni alloy, Fe-Si-Cr alloy, Fe-Si-Al-Ni-Cr alloy, Fe-Cr-Al-Ni-Cr alloy, Fe-Cr-Al-Cr-Fe-Cr alloy, and Fe₂O₃、Fe₃O₄At least one magnetic particle selected from the group consisting of Mn-Zn-based ferrites, Ni-Zn-based ferrites, Mg-Mn-based ferrites, Zr-Mn-based ferrites, Ti-Mn-based ferrites, Mn-Zn-Cu-based ferrites, barium ferrites, and strontium ferrites.

＜8＞

The maleimide resin film according to any one of < 1 > - < 4 >, wherein,

(c) the inorganic particles of component (B) are white particles of at least one selected from titanium dioxide, yttrium oxide, zinc sulfate, zinc oxide and magnesium oxide.

＜9＞

The maleimide resin film according to any one of < 1 > - < 4 >, wherein,

(c) the inorganic particles of component (B) are at least one hollow particle selected from the group consisting of silica hollow spheres, carbon hollow spheres, alumina silicate hollow spheres and zirconia hollow spheres.

＜10＞

The maleimide resin film according to any one of < 1 > - < 4 >, wherein,

(c) the inorganic particles of the component (A) are selected from carbon black, acetylene black, ketjen black, carbon nanotubes, graphene, fullerene, carbonyl iron, electrolytic iron, Fe-Cr-based alloy, Fe-Al-based alloy, Fe-Co-based alloy, Fe-Cr-Al-based alloy, Fe-Si-Ni-based alloy, Mg-Zn-based ferrite, Ba₂Co₂Fe₁₂O₂₂、Ba₂Ni₂Fe₁₂O₂₂、Ba₂Zn₂Fe₁₂O₂₂、Ba₂Mn₂Fe₁₂O₂₂、Ba₂Mg₂Fe₁₂O₂₂、Ba₂Cu₂Fe₁₂O₂₂、Ba₃Co₂Fe₂₄O₄₁、BaFe₁₂O₁₉、SrFe₁₂O₁₉、BaFe₁₂O₁₉And SrFe₁₂O₁₉At least one electromagnetic wave absorbing particle.

＜11＞

A composition for a maleimide resin film, which is a maleimide resin composition constituting the maleimide resin film described in any one of < 1 > -to < 10 >,

the composition further comprises (e) an organic solvent, and the thixotropic ratio of the resin composition at 25 ℃ is 1.0-3.0.

ADVANTAGEOUS EFFECTS OF INVENTION

The maleimide resin film of the present invention has excellent adhesion even when highly filled with inorganic particles. Therefore, the resin film having various functionalities depending on the characteristics of the inorganic particles to be blended can be used for various applications. When the inorganic particles do not have conductivity, the inorganic particles can be used as an adhesive resin film having low dielectric properties.

Detailed Description

The maleimide resin film of the present invention will be described in detail below.

[ (a) Maleimide ]

The component (a) of the present invention is a main component of the maleimide resin film of the present invention, and is a maleimide represented by the following formula (1).

(in the formula (1), A independently represents a 4-valent organic group containing a cyclic structure, B independently represents an alkylene group having 1 or more aliphatic rings having 5 or more carbon atoms and optionally containing a heteroatom and having 6 or more carbon atoms, Q independently represents an arylene group having 6 or more carbon atoms and optionally containing a heteroatom, W represents a group represented by B or Q, n is 0 to 100, and m represents a number of 0 to 100, wherein at least one of n and m is a positive number.)

The organic group represented by a in formula (1) is independently a tetravalent organic group having a cyclic structure, and particularly preferably any of the tetravalent organic groups represented by the following structural formulae.

(the bonding position of the unbonded substituent in the above formula is bonded to the carbonyl carbon forming the cyclic imide structure in formula (1).)

In addition, B in formula (1) is independently an alkylene group having 6 or more, preferably 8 or more carbon atoms optionally containing a hetero atom, and is an alkylene group having 1 or more aliphatic rings having 5 or more, preferably 6 to 12 carbon atoms. B in formula (1) is more preferably any alkylene group among alkylene groups having an aliphatic ring represented by the following structural formula. The composition can contain the inorganic particles (c) highly filled with the aliphatic ring in the molecule.

(the bonding position of the unbonded substituent in the above structural formula is bonded to the nitrogen atom forming the cyclic imide structure in formula (1))

Q is independently an arylene group having 6 or more carbon atoms, preferably 8 or more carbon atoms, which may optionally contain a hetero atom. Q in formula (1) is more preferably any arylene group among arylene groups having an aromatic ring represented by the following structural formula.

N in the formula (1) is a number of 0 to 100, preferably a number of 0 to 70. M in the formula (1) is a number of 0 to 100, preferably a number of 0 to 70. Wherein at least one of n and m is a positive number.

The molecular weight of the maleimide is not particularly limited, but is preferably 2000 to 50000, more preferably 2200 to 30000, and further preferably 2500 to 20000. When the molecular weight of the component (a) is within this range, the viscosity of the composition for producing a maleimide resin film is not excessively high, and further, the cured product of the resin film has high strength, which is preferable.

The molecular weight referred to in the present specification means a weight average molecular weight of polystyrene measured by GPC under the following conditions as a standard substance.

[ measurement conditions ]

Developing solvent: tetrahydrofuran (THF)

Flow rate: 0.35mL/min

A detector: RI (Ri)

Column: TSK-GEL Super HZ model (manufactured by TOSOH CORPORATION)

SuperHZ4000(4.6mm I.D.×15cm×1)

SuperHZ3000(4.6mm I.D.×15cm×1)

SuperHZ2000(4.6mm I.D.×15cm×1)

Column temperature: 40 deg.C

Sample injection amount: 5 μ L (0.1% strength by weight in THF)

The amount of the maleimide to be blended is not particularly limited, and is 50 to 99 parts by mass, preferably 60 to 95 parts by mass, and more preferably 70 to 90 parts by mass, based on 100 parts by mass of the resin film. When the content is within this range, the inorganic particles of component (c) can be highly filled and the resin film has sufficient adhesive strength.

As the maleimide, it can be synthesized from a diamine and an acid anhydride by a conventional method, and a commercially available product can also be used. Commercially available products include BMI-1400, BMI-1500, BMI-2500, BMI-2560, BMI-3000, BMI-5000, BMI-6000, and BMI-6100 (all of which are manufactured by Designer polymers Inc.). In addition, the maleimide may be used singly or in combination of two or more.

The amount of component (a) is preferably 40 to 95 parts by mass, more preferably 50 to 90 parts by mass, and still more preferably 70 to 90 parts by mass, per 100 parts by mass of resin in the resin film. The resin content of the resin film is the sum of the components (a), (b), and (d).

[ (b) a (meth) acrylate having 10 or more carbon atoms ]

(b) The component (a) is a compound which has good compatibility with inorganic particles, and can further improve the adhesive strength of a resin film, similarly to the maleimide of the component (a).

(b) The component (B) is a (meth) acrylate having 10 or more carbon atoms, preferably a (meth) acrylate having 12 or more carbon atoms, and more preferably a (meth) acrylate having 14 to 40 carbon atoms. If the number of carbon atoms of the (meth) acrylate is less than 10, it is difficult to obtain an effect of improving the adhesion of the resin film or the like, and the flexibility of the uncured resin film cannot be further improved.

The number of (meth) acrylic acid groups in one molecule of the component (b) is not particularly limited, and is 1 to 3, preferably 1 or 2. When the number of (meth) acrylic acid groups in 1 molecule of the component (b) is 1 to 3, shrinkage of the resin film during curing is small and the adhesive force is not reduced, which is preferable.

Specific examples of the component (b) include, but are not limited to, compounds represented by the following structural formulae.

(in the above formula, x is in the range of 1 to 30, respectively.)

(in the above formula, x is in the range of 1 to 30.)

In the above examples, the component (b) is preferably an aliphatic ring having one or more carbon atoms of 5 or more, preferably 6 to 12, in one molecule.

The amount of the component (b) is not particularly limited, and is 1 to 50 parts by mass, preferably 3 to 30 parts by mass, and more preferably 5 to 20 parts by mass, based on 100 parts by mass of the resin film. When the content is within this range, the inorganic particles of component (c) can be highly filled and the resin film has sufficient adhesive strength.

[ (c) inorganic particles ]

The component (c) used in the present invention is a component for determining the characteristics of the maleimide-based resin film of the present invention, and examples thereof include: conductive particles, heat conductive particles, fluorescent materials, magnetic particles, white particles, hollow particles, electromagnetic wave absorbing particles, and the like.

The conductive particles are not particularly limited and may be appropriately selected depending on the intended purpose. For example, metal particles, metal-coated particles, and the like can be cited. Among these, metal particles are preferable because they have low electrical resistance and can be sintered at high temperature.

The metal particles include simple metal particles such as gold, silver, copper, palladium, aluminum, nickel, iron, titanium, manganese, zinc, tungsten, platinum, lead, and tin, or alloys such as solder, steel, and stainless steel, preferably silver, copper, aluminum, iron, zinc, and solder, and more preferably silver, copper, aluminum, and solder. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Examples of the metal-coated particles include those in which the surface of resin particles such as acrylic resin and epoxy resin is coated with a metal, and those in which the surface of inorganic particles such as glass and ceramics is coated with a metal. The method of coating the metal on the particle surface is not particularly limited, and examples thereof include: chemical plating, sputtering, and the like.

Examples of the metal coating the particle surface include gold, silver, copper, iron, nickel, and aluminum.

The conductive particles may have conductivity when electrically connected to the circuit electrode. For example, even in the case of particles having an insulating coating on the particle surface, conductive particles are obtained by deforming the particles and exposing the metal particles during electrical connection.

The shape of the conductive particles is not particularly limited, and examples thereof include: spherical, scaly, flaky, needle-like, rod-like, oval, and the like. Among them, preferred are a spherical shape, a scaly shape, an elliptical shape, and a rod shape, and more preferred are a spherical shape, a scaly shape, and an elliptical shape.

The average particle diameter of the conductive particles is not particularly limited, and the median particle diameter measured by a particle size distribution measuring apparatus using a laser diffraction method is preferably 0.05 to 50 μm, more preferably 0.1 to 40 μm, and still more preferably 0.5 to 30 μm. Within this range, the conductive particles are easily and uniformly dispersed in the resin film, and the conductive particles are preferably free from sedimentation, separation, and unevenness with time. The particle diameter is preferably 50% or less with respect to the thickness of the film. When the particle diameter is 50% or less with respect to the thickness of the film, the conductive particles can be easily uniformly dispersed in the resin film, and a flat film can be easily obtained, which is preferable.

The thermally conductive particles are not particularly limited, but are preferably at least one selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, beryllium oxide, magnesium oxide, zinc oxide, aluminum oxide, silicon carbide, diamond, and graphene in view of thermal conductivity. Among them, boron nitride, aluminum oxide, magnesium oxide, and graphene are preferable. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.

The shape of the thermal conductive particles is not particularly limited, and examples thereof include: spherical, scaly, flaky, needle-like, rod-like, oval, and the like. Among them, preferred are a spherical shape, a scaly shape, an elliptical shape, and a rod shape, and more preferred are a spherical shape, a scaly shape, and an elliptical shape.

The average particle diameter of the thermally conductive particles is not particularly limited, and the median particle diameter measured by a particle size distribution measuring apparatus using a laser diffraction method is preferably 0.05 to 50 μm, more preferably 0.1 to 40 μm, and still more preferably 0.5 to 30 μm. Within this range, the thermally conductive particles are easily uniformly dispersed in the resin film, and the thermally conductive particles are preferably free from sedimentation, separation, and unevenness with time. The particle diameter is preferably 50% or less with respect to the thickness of the film. When the particle diameter is preferably 50% or less with respect to the thickness of the film, the thermally conductive particles can be easily uniformly dispersed in the resin film, and a flat film can be more easily obtained, which is preferable.

As the phosphor, for example, a phosphor that absorbs light from a semiconductor light emitting diode having a nitride semiconductor as a light emitting layer and changes its wavelength to light of a different wavelength can be used. Examples of such a phosphor include: nitride phosphors and oxynitride phosphors activated mainly by lanthanum elements such as Eu and Ce; alkaline earth halogen apatite phosphor, alkaline earth metal borate halogen phosphor, alkaline earth metal aluminate phosphor, alkaline earth metal silicate phosphor, alkaline earth metal sulfide phosphor, rare earth sulfide phosphor, alkaline earth metal thiogallate phosphor, alkaline earth metal alkaline earth silicon nitride phosphor, and germanate phosphor activated mainly with a lanthanum-based element such as Eu or a transition metal-based element such as Mn; rare earth aluminate phosphor and rare earth silicate phosphor mainly activated by lanthanum elements such as Ce; Ca-Al-Si-O-N oxynitride glass phosphor activated mainly by a lanthanum-based element such as Eu. These phosphors may be used alone in 1 kind, or in combination of 2 or more kinds. As a specific example, the following phosphors can be exemplified, but the phosphors are not limited thereto.

As the nitride-based phosphor activated mainly by a lanthanum-based element such as Eu or Ce, M can be exemplified₂Si₅N₈：Eu、MSi₇N₁₀：Eu、M_1.8Si₅O_0.2N₈：Eu、M_0.9Si₇O_0.1N₁₀: eu (M is at least one selected from Sr, Ca, Ba, Mg and Zn).

As the oxynitride phosphor mainly activated by a lanthanum-based element such as Eu or Ce, M can be exemplified₂Si₂N₂: eu (M is at least one selected from Sr, Ca, Ba, Mg and Zn).

As the alkaline earth halogen apatite phosphor activated mainly by a lanthanum group element such as Eu or a transition metal group element such as Mn, M can be exemplified₅(PO₄)₃X: z (M is at least one selected from Sr, Ca, Ba and Mg, X is at least one selected from F, Cl, Br and I, Z is at least one selected from Eu and manganese) and the like.

As the alkaline earth metal borate halogen phosphor activated mainly by a lanthanum-based element such as Eu or a transition metal-based element such as Mn, M can be exemplified₂B₅O₉X: z (M is more than one selected from Sr, Ca, Ba and Mg, X is more than one selected from F, Cl, Br and I, Z is more than one selected fromEu, Mn, and one or more of Eu and Mn).

As the alkaline earth metal aluminate phosphor activated mainly by a lanthanum-based element such as Eu or a transition metal-based element such as Mn, SrAl can be exemplified₂O₄：Z、Sr₄Al₁₄O₂₅：Z、CaAl₂O₄：Z、BaMg₂Al₁₆O₂₇：Z、BaMg₂Al₁₆O₁₂：Z、BaMgAl₁₀O₁₇: z (Z is at least one selected from Eu and Mn), and the like.

As the alkaline earth metal silicate phosphor activated mainly by a lanthanum-based element such as Eu or a transition metal-based element such as Mn, (BaMg) Si is exemplified₂O₅: eu and (BaSrCa)₂SiO₄: eu, and the like.

Examples of the alkaline earth metal sulfide phosphor activated mainly by a lanthanum-based element such as Eu and a transition metal-based element such as Mn include (Ba, Sr, Ca) (Al, Ga)₂S₄: eu, and the like.

As the rare earth sulfide phosphor activated mainly by a lanthanum-based element such as Eu or a transition metal-based element such as Mn, La can be exemplified₂O₂S：Eu、Y₂O₂S: eu and Gd₂O₂S: eu, and the like.

An example of the alkaline earth metal thiogallate phosphor activated mainly by a lanthanum-based element such as Eu or a transition metal-based element such as Mn is MGa₂S₄: eu (M is at least one selected from Sr, Ca, Ba, Mg and Zn).

Examples of the alkaline earth metal silicon nitride phosphor activated mainly by a lanthanum-based element such as Eu and a transition metal-based element such as Mn include (Ca, Sr, Ba) AlSiN₃：Eu、(Ca、Sr、Ba)₂Si₅N₈: eu and SrAlSi₄N₇: eu, and the like.

As germanate phosphors activated mainly by lanthanum-based elements such as Eu and transition metal-based elements such as Mn, Zn can be exemplified₂GeO₄: mn and the like.

As the rare earth aluminate phosphor activated mainly by lanthanum group element such as Ce, Y can be exemplified₃Al₅O₁₂：Ce、(Y_0.8Gd_0.2)₃Al₅O₁₂：Ce、Y₃(Al_0.8Ga_0.2)₅O₁₂: ce and (Y, Gd)₃(Al、Ga)₅O₁₂And YAG based phosphors. Tb in which Tb or Lu is substituted for a part or all of Y may be used₃Al₅O₁₂: ce and Lu₃Al₅O₁₂: ce, and the like.

As the rare earth silicate phosphor mainly activated by lanthanum group element such as Ce, Y can be exemplified₂SiO₅: ce and Tb, etc.

The Ca-Al-Si-O-N oxynitride glass phosphor is represented by the following formula (I) CaCO₃20 to 50 mol% of Al in terms of CaO₂O₃0 to 30 mol%, 25 to 60 mol% of SiO, 5 to 50 mol% of AlN, 0.1 to 20 mol% of a rare earth oxide or a transition metal oxide, and 100 mol% of a total of 5 components. In the phosphor using oxynitride glass as a matrix material, the nitrogen content is preferably 15 mass% or less. In addition, it is preferable that the phosphor contains rare earth element ions other than the rare earth oxide ions as a sensitizer in the state of the rare earth oxide, and the phosphor contains the rare earth element ions as a co-activator in a content of 0.1 to 10 mol%.

As other phosphors, ZnS: eu, and the like. In addition, examples of the silicate-based phosphor other than the above include (BaSrMg)₃Si₂O₇：Pb、(BaMgSrZnCa)₃Si₂O₇：Pb、Zn₂SiO₄: mn and BaSi₂O₅: pb, and the like.

In addition, the phosphor may contain one or more phosphors selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, and Ti in addition to or instead of Eu.

In addition, if the phosphor is a phosphor other than the above-mentioned phosphor and has the same performance and effect as those described above, the phosphor can be used as the inorganic particles in the present invention.

The characteristics of the phosphor are not particularly limited, and for example, a phosphor in a powder form can be used. The shape of the phosphor powder is not particularly limited, and examples thereof include: spherical, scaly, flaky, needle-like, rod-like, oval, and the like. Among them, preferred are a spherical shape, a scaly shape and a flaky shape, and more preferred are a spherical shape and a flaky shape.

The particle size of the phosphor is not particularly limited, but is preferably 0.05 to 50 μm, more preferably 0.1 to 40 μm, and even more preferably 0.5 to 30 μm as a median particle size measured by a particle size distribution measuring apparatus using a laser diffraction method. Within this range, the phosphor is easily uniformly dispersed in the resin film, and the phosphor is preferably free from sedimentation, separation, and unevenness with time. Further, the particle diameter is preferably 50% or less with respect to the thickness of the film. When the particle diameter is preferably 50% or less with respect to the thickness of the film, the phosphor can be easily uniformly dispersed in the resin film, and a flat film can be easily obtained, which is preferable.

The magnetic particles are not particularly limited, and it is preferable to use a strong magnetic metal simple substance such as iron, cobalt, and nickel; magnetic metal alloys such as stainless steel, Fe-Cr-Al-Si alloy, Fe-Si-Al alloy, Fe-Ni alloy, Fe-Cu-Si alloy, Fe-Si-B (-Cu-Nb) alloy, Fe-Si-Cr-Ni alloy, Fe-Si-Cr alloy, and Fe-Si-Al-Ni-Cr alloy; hematite (Fe)₂O₃) Magnetite (Fe)₃O₄) And the like metal oxides; ferrites such as Mn-Zn ferrite, Ni-Zn ferrite, Mg-Mn ferrite, Zr-Mn ferrite, Ti-Mn ferrite, Mn-Zn-Cu ferrite, barium ferrite, and strontium ferrite.

By blending the magnetic particles, the resin composition of the present invention can be provided with magnetic properties, and thus can be a resin composition having high magnetic permeability and low loss in a high frequency band region.

The shape of the magnetic particles is not particularly limited, and examples thereof include: spherical, scaly, flaky, needle-like, rod-like, oval, porous, etc. Among them, preferred are spherical, scaly, elliptical, flaky, and porous shapes, and more preferred are spherical, scaly, flaky, and porous shapes.

When porous magnetic particles are obtained, they can be obtained by a method in which a cell regulator such as calcium carbonate is added during granulation, granulation is performed, and firing is performed. Further, by adding a material that suppresses particle growth in the ferrite reaction, complicated voids can be formed inside the ferrite. Examples of such a material include tantalum oxide and zirconium oxide.

The particle size of the magnetic particles is not particularly limited, but is preferably 0.05 to 50 μm, more preferably 0.1 to 40 μm, and even more preferably 0.5 to 30 μm, as the median particle size measured by a particle size distribution measuring apparatus using a laser diffraction method. Within this range, it is preferable that the magnetic particles are easily uniformly dispersed in the resin film, and that the magnetic particles are not sedimented, separated, or unevenly distributed with time. When the film is processed into a film shape, the particle diameter is preferably 50% or less with respect to the thickness of the film. When the particle diameter is 50% or less with respect to the thickness of the film, the magnetic particles can be easily uniformly dispersed in the resin film, and a flat film can be easily obtained, which is preferable.

The white particles are blended in order to improve whiteness required for applications such as reflection. Examples of the white pigment include rare earth oxides typified by titanium dioxide and yttrium oxide, zinc sulfate, zinc oxide, and magnesium oxide. These may be used alone or in combination. Among them, titanium dioxide is preferably used in order to further improve whiteness. The unit cell of the titanium dioxide has a rutile type, an anatase type, and a brookite type, and any of them can be used. However, from the viewpoint of whiteness and photocatalytic activity of titanium dioxide, rutile type is preferably used.

The shape of the white particles is not particularly limited, and examples thereof include: spherical, scaly, flaky, needle-like, rod-like, oval, and the like. Among them, the spherical, elliptical and plate-like shapes are preferable, and the spherical shape is more preferable.

The average particle diameter of the white particles is not particularly limited, and is preferably 0.05 to 5 μm, more preferably 3 μm or less, and even more preferably 1 μm or less, as a median diameter measured by a particle size distribution measuring apparatus using a laser diffraction method. When the film is processed into a film shape, the particle diameter is preferably 50% or less with respect to the thickness of the film. When the particle diameter is 50% or less with respect to the thickness of the film, white particles can be easily uniformly dispersed in the resin film, and a flat film can be easily obtained, which is preferable.

In order to improve wettability, compatibility, dispersibility, and fluidity with the resin, the white particles are preferably surface-treated white particles, and more preferably surface-treated with at least one or more selected from silica, alumina, zirconia, a polyol, and an organosilicon compound, particularly two or more of these treating agents.

In addition, titanium dioxide treated with an organosilicon compound is preferable in order to improve the initial reflectance and improve the fluidity of the resin composition containing the white particles. Examples of the organosilicon compound include monomeric organosilicon compounds such as chlorosilane, silazane, and silane coupling agents having reactive functional groups such as epoxy group and amino group, and organopolysiloxanes such as silicone oil and silicone resin. Other treating agents generally used for surface treatment of titanium dioxide, such as organic acids like stearic acid, may be used, surface treatment with other treating agents than those described above may be performed, or surface treatment with a plurality of treating agents may be performed.

The hollow particles are not particularly limited, and examples thereof include: silica hollow spheres, carbon hollow spheres, alumina hollow spheres, aluminosilicate hollow spheres, and the like.

The shape of the hollow particles is not particularly limited, and examples thereof include: spherical, elliptical, cylindrical, prismatic, etc. Among them, spherical, elliptical, and prismatic shapes are preferable, and spherical and prismatic shapes are more preferable.

The average particle diameter of the hollow particles is not particularly limited, but is preferably 0.01 to 5 μm, more preferably 0.03 to 3 μm, and still more preferably 0.05 to 1 μm, as a median diameter measured by a laser diffraction particle size distribution measuring apparatus. Further, the particle diameter is preferably 50% or less with respect to the thickness of the film. When the particle diameter is 50% or less with respect to the thickness of the film, the hollow particles can be easily uniformly dispersed in the resin film, and a flat film can be easily obtained, which is preferable.

By blending the hollow particles, the specific gravity of the cured product of the resin composition of the present invention can be easily reduced, and the weight can be reduced.

The electromagnetic wave absorbing particles are not particularly limited, and can be used for dielectric loss electromagnetic wave absorbing materials represented by conductive particles and carbon particles, magnetic loss electromagnetic wave absorbing materials represented by ferrite and soft magnetic metal powder, and the like.

By blending the electromagnetic wave absorbing particles, the resin composition of the present invention can be provided with electromagnetic wave absorbing ability, and a cured resin having electromagnetic wave shielding properties such as a case of an electronic device can be easily obtained.

Examples of the dielectric loss electromagnetic wave absorbing material include simple metal substances such as gold, silver, copper, palladium, aluminum, nickel, iron, titanium, manganese, zinc, tungsten, platinum, lead, and tin, conductive particles such as solder, steel, and stainless steel, and carbon particles such as carbon black, acetylene black, ketjen black, carbon nanotubes, graphene, and fullerene. Among them, carbon black, acetylene black, ketjen black, carbon nanotubes, graphene, and fullerene are preferable.

Examples of the dielectric loss electromagnetic wave absorbing material include Mg-Zn ferrite and Ba₂Co₂Fe₁₂O₂₂、Ba₂Ni₂Fe₁₂O₂₂、Ba₂Zn₂Fe₁₂O₂、Ba₂Mn₂Fe₁₂O₂₂、Ba₂Mg₂Fe₁₂O₂₂、Ba₂Cu₂Fe₁₂O₂₂、Ba₃Co₂Fe₂₄O₄₁、BaFe₁₂O₁₉、SrFe₁₂O₁₉、BaFe₁₂O₁₉And SrFe₁₂O₁₉Ferrite particles, etc.; soft magnetic alloy particles such as carbonyl iron, electrolytic iron, Fe-Cr alloy, Fe-Si alloy, Fe-Ni alloy, Fe-Al alloy, Fe-Co alloy, Fe-Al-Si alloy, Fe-Cr-Al alloy, Fe-Si-Ni alloy, and Fe-Si-Cr-Ni alloy. Among them, preferred is a ferrite selected from the group consisting of Mg-Zn-based ferrites and Ba₂Co₂Fe₁₂O₂₂、Ba₂Ni₂Fe₁₂O₂₂、Ba₂Zn₂Fe₁₂O₂、Ba₂Mn₂Fe₁₂O₂₂、Ba₂Mg₂Fe₁₂O₂₂、Ba₂Cu₂Fe₁₂O₂₂、Ba₃Co₂Fe₂₄O₄₁、BaFe₁₂O₁₉、SrFe₁₂O₁₉、BaFe₁₂O₁₉And SrFe₁₂O₁₉At least one of (1).

These electromagnetic wave absorbing particles may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The shape of the electromagnetic wave absorbing particles is not particularly limited, and examples thereof include: spherical, scaly, flaky, needle-like, rod-like, oval, and the like. Among them, preferred are a spherical shape, a scaly shape, an elliptical shape, and a rod shape, and more preferred are a spherical shape, a scaly shape, and an elliptical shape.

The particle diameter of the electromagnetic wave absorbing particles is not particularly limited, but is preferably 0.05 to 50 μm, more preferably 0.1 to 40 μm, and further preferably 0.5 to 30 μm or less as the median diameter measured by a laser diffraction particle size distribution measuring apparatus. Within this range, the electromagnetic wave absorbing particles are easily uniformly dispersed in the resin film, and the electromagnetic wave absorbing particles are not precipitated, separated, or non-uniform with the passage of time, which is preferable. Further, the particle diameter is preferably 50% or less with respect to the thickness of the film. When the particle diameter is 50% or less with respect to the thickness of the film, the electromagnetic wave absorbing particles can be easily uniformly dispersed in the resin film, and the film can be easily coated flatly, which is preferable.

In order for the resin film to function as inorganic particles, it is important not to mass% of the inorganic particles but to volume% of the inorganic particles, and it is preferable to highly fill the resin film with the inorganic particles as much as possible. The inorganic particles are incorporated in an amount of 70 to 90 vol%, preferably 72 to 88 vol%, more preferably 75 to 85 vol% of the entire resin film. When the content is less than 70% by volume, the function of the inorganic particles cannot be sufficiently exerted; when the content is more than 90 vol%, a cured product of the resin film becomes brittle and adhesive strength becomes weak.

[ (d) curing catalyst ]

The component (d) used in the present invention is a catalyst for curing the maleimide resin film. The curing catalyst is not particularly limited, and examples thereof include a thermal radical polymerization initiator, a thermal cationic polymerization initiator, a thermal anionic polymerization initiator, and a photopolymerization initiator.

Examples of the thermal radical polymerization initiator include: methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methylacetoacetic acid peroxide, acetylacetone peroxide, 1-bis (t-butylperoxy) 3,3, 5-trimethylcyclohexane, 1-bis (t-hexylperoxy) cyclohexane, 1-bis (t-hexylperoxy) 3,3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) cyclohexane, 2-bis (4, 4-di-t-butylperoxycyclohexyl) propane, 1-bis (t-butylperoxy) cyclododecane, n-butyl 4, 4-bis (t-butylperoxy) valerate, 2-bis (t-butylperoxy) butane, 1-bis (t-butylperoxy) -2-methylcyclohexane, t-butylhydroperoxide, P-menthane hydroperoxide, 1,3, 3-tetramethylbutyl hydroperoxide, t-hexylhydroperoxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, α' -bis (t-butylperoxy) diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5, 5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-tert-hexylhydroperoxide, dicumyl peroxide, di-2-ethylhexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, α' -bis (peroxyneodecanoyl) diisopropylbenzene, cumyl peroxyneodecanoate, 1,3, 3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, 2, 5-dimethyl-2, 5-bis (2-ethylhexanoic acid peroxy) hexane, 1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate, di-tert-butyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di (4-butyl, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexyl ester, tert-hexyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexyl ester, tert-butyl peroxy isobutyrate, tert-butyl peroxy maleate, tert-butyl peroxy dodecanoate, tert-butyl peroxy-3, 5, 5-trimethylhexyl tert-butyl ester, tert-butylperoxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, 2, 5-dimethyl-2, 5-bis (benzoyl peroxide) hexane, tert-butyl peroxy acetate, tert-hexyl peroxy benzoate, tert-butyl m-toluoylbenzoate, tert-butyl peroxybenzoate, bis (tert-butylperoxy) isophthalate, tert-butyl peroxy allyl monocarbonate, 3, organic peroxides such as 3', 4, 4' -tetrakis (t-butylperoxycarbonyl) benzophenone; 2,2 '-azobis (N-butyl-2-methylpropionamide), 2' -azobis (N-cyclohexyl-2-methylpropionamide), 2 '-azobis [ N- (2-methylpropyl)) -2-methylpropionamide ], 2' -azobis [ N- (2-methylethyl) -2-methylpropionamide ], 2 '-azobis (N-hexyl-2-methylpropionamide), 2' -azobis (N-propyl-2-methylpropionamide), 2 '-azobis (N-ethyl-2-methylpropionamide), 2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], (N-methyl-N-2-methylpropionamide), Azo compounds such as 2,2 '-azobis [ N- (2-propenyl) -2-methylpropionamide ], 2' -azobis { 2-methyl-N-1, 1-bis (hydroxymethyl) -2-hydroxyethyl ] propionamide }, 2 '-azobis [ N- (2-propenyl) -2-methylpropionamide ], dimethyl-1, 1' -azo (1-cyclohexane carboxylate), and the like. Preferred examples thereof include dicumyl peroxide, di-t-butyl peroxide, isobutyryl peroxide, 2 '-azobis (N-butyl-2-methylpropionamide) and 2, 2' -azobis [ N- (2-methylethyl) -2-methylpropionamide ], and more preferred examples thereof include dicumyl peroxide, di-t-butyl peroxide and isobutyryl peroxide.

Examples of the thermal cationic polymerization initiator include: (4-methylphenyl) [4- (2-methylpropyl) phenyl group]Iodine

Cation, (4-methylphenyl) (4-isopropylphenyl) iodine

Cation, (4-methylphenyl) (4-isobutyl) iodide

Cationic, bis (4-tert-butyl) iodide

Cationic bis (4-dodecylphenyl) iodide

Cation, (2,4, 6-trimethylphenyl) [4- (1-methyl ethyl acetate) phenyl]Iodine

Aromatic iodine such as cation

Salt; diphenyl [4- (phenylthio) phenyl]Aromatic sulfonium salts such as sulfonium cation, triphenylsulfonium cation, and alkyltriphenylsulfonium cation. Among them, (4-methylphenyl) [4- (2-methylpropyl) phenyl ] is preferred]Iodine

Cation, (4-methylphenyl) (4-isopropylphenyl) iodine

A cation, a triphenylsulfonium cation, an alkyltriphenylsulfonium cation, more preferably (4-methylphenyl) [4- (2-methylpropyl) phenyl ]]Iodine

Cation, (4-methylphenyl) (4-isopropylphenyl) iodine

A cation.

Examples of the thermal anionic polymerization initiator include: imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; amines such as triethylamine, triethylenediamine, 2- (dimethylaminomethyl) phenol, 1, 8-diazabicyclo [5.4.0] undecene-7, tris (dimethylaminomethyl) phenol, and benzyldimethylamine; phosphines such as triphenylphosphine, tributylphosphine, and trioctylphosphine. Among them, 2-methylimidazole, 2-ethyl-4-methylimidazole, triethylamine, triethylenediamine, 1, 8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, and tributylphosphine are preferable, and 2-ethyl-4-methylimidazole, 1, 8-diazabicyclo [5.4.0] undecene-7, and triphenylphosphine are more preferable.

The photopolymerization initiator is not particularly limited, and examples thereof include benzoyl compounds (or benzophenone compounds) such as benzophenone, particularly benzoyl compounds (or benzophenone compounds) having a carbonyl group on the carbon atom at the α -position of the hydroxyl group such as 1-hydroxyhexyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- (4-isopropylphenyl) -2-carbonyl-2-methylpropan-1-one; α -alkylaminobenzone compounds such as 2-methyl-1- (4-methylthiophenyl) -2-methylmorpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butan-1-one, and 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholinyl-4-phenyl) -butan-1-one; acylphosphine oxide compounds such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bisacylmonoorganylphosphine oxide, bis (2, 6-dioxobenzoyl) -2,4, 4-trimethylpentylphosphine oxide and the like; benzoin ether compounds such as isobutyl benzoin ether; ketal compounds such as acetophenone diethyl ketal; thioxanthone compounds; acetophenone compounds, and the like.

In particular, since the radiation emitted from the UV-LED has a single wavelength, when the UV-LED is used as a light source, it is effective to use a photopolymerization initiator using an α -alkylaminophenol compound or acylphosphine oxide compound having an absorption spectrum peak in a region of 340 to 400 nm.

These (d) components can be used alone in 1 kind, also can be combined with more than 2 kinds.

(d) The content of the component (d) is not particularly limited, and is 0.01 to 10 parts by mass, preferably 0.05 to 8 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the resin film. If within this range, the maleimide resin film can be sufficiently cured.

The maleimide resin film of the present invention may further contain, in addition to the above components (a) to (d), an adhesive aid, an antioxidant, a flame retardant, and the like, as required. Hereinafter, each component will be described.

[ adhesion promoters ]

The adhesion aid is not particularly limited, and examples thereof include: silane coupling agents such as n-propyltrimethoxysilane, n-propyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 2- [ methoxy (polyoxyethylene) propyl ] -trimethoxysilane, methoxytris (oxyethylene) propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane and glycidoxypropyltrimethoxysilane, and the like, Isocyanurate compounds such as triallylisocyanurate and triglycidyl isocyanurate.

The content of the bonding aid is not particularly limited, and is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and still more preferably 1 to 5 parts by mass, based on 100 parts by mass of the resin component of the resin film. When the content is within this range, the adhesive strength of the resin film can be further improved without changing the physical properties of the resin film.

[ antioxidant ]

The antioxidant is not particularly limited, and examples thereof include: n-octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, n-octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acetate, neododecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, dodecyl-4- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, ethyl-. alpha. - (4-hydroxy-3, 5-di-tert-butylphenyl) isobutyrate, octadecyl-. alpha. - (4-hydroxy-3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, n-octadecyl-3- (3, 5-di-tert-butyl-4-, Phenol antioxidants such as 2- (n-octylthio) ethyl-3, 5-di-tert-butyl-4-hydroxyphenyl acetate, 2- (n-octadecylthio) ethyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2- (2-stearoyloxyethylthio) ethyl-7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate, and 2-hydroxyethyl-7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate; sulfur antioxidants such as dilauryl-3, 3 '-thiodipropionate, dimyristyl-3, 3' -thiodipropionate, distearyl-3, 3 '-thiodipropionate, ditridecyl-3, 3' -thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate); phosphorus antioxidants such as tridecyl phosphite, triphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, 2-ethylhexyl diphenyl phosphite, ditolyl tridecyl diphenylphosphite, 2-methylenebis (4, 6-dibutylphenyl) octyl phosphite, distearyl pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxaphosphin-6-yl ] oxy ] -N, N-bis [2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxaphosphin-6-yl ] oxy ] -ethyl ] ethylamine and the like .

The content of the antioxidant is not particularly limited, and is preferably 0.00001 to 5 parts by mass, more preferably 0.0001 to 4 parts by mass, and still more preferably 0.001 to 3 parts by mass, based on 100 parts by mass of the resin component of the resin film. If the amount of the antioxidant is within this range, the oxidation of the resin film can be prevented without changing the mechanical properties of the resin film.

[ flame retardant ]

The flame retardant is not particularly limited, and examples thereof include: phosphorus flame retardants, metal hydrates, halogen flame retardants, and the like. Examples thereof include: phosphorus compounds such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate and the like, inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide and the like, phosphoric acid, phosphine oxide, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyldi-2, 6-xylenyl phosphate, resorcinol bis (diphenyl phosphate), 1, 3-phenylene bis (di-2, 6-xylenyl phosphate), bisphenol a-bis (diphenyl phosphate), 1, 3-phenylene bis (diphenyl phosphate), phenyl phosphonic acid divinyl ester, phenyl phosphonic acid diallyl ester, phenyl phosphonic acid bis (1-butene) ester, phenyl diphenylphosphonate, methyl diphenylphosphonate, bis (2-allylphenoxy) phosphazene, xylenol phosphazene and the like; melamine phosphate; melamine pyrophosphate; melamine polyphosphate, phosphorus flame retardants such as 9, 10-dihydroxy-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydroxy-9-oxa-10-phosphaphenanthrene-10-oxide, metal hydrates such as aluminum hydroxide hydrate and magnesium hydroxide hydrate, hexabromobenzene, pentabromotoluene, ethylene bis (pentabromophenyl), ethylene bis-tetrabromophthalimide, 1, 2-dibromo-4- (1, 2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene, 2,4, 6-tris (tribromophenoxy) -1, halogen flame retardants such as 3, 5-triazine.

The content of the flame retardant is not particularly limited, but is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and still more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the resin component of the resin film. If the amount of the flame retardant is within this range, flame retardancy can be imparted to the resin film without changing the mechanical properties of the resin film.

[ Maleimide resin film ]

The method for molding the resin film of the present invention is not particularly limited, and examples thereof include a method in which the maleimide resin composition constituting the resin film (i.e., the maleimide resin composition containing the components (a), (b), (c) and (d)) is cast onto a film having releasability, and the like, and then subjected to doctor blading (squeegee).

In this case, the maleimide resin composition is preferably one having a low viscosity by heating, solvent dilution or the like, and more preferably one containing an organic solvent (e) described later. In the case of dilution with an organic solvent, if the thixotropic ratio of the composition after dilution is within a range of 1.0 to 3.0, the processability is good, and therefore, it is preferably within a range of 1.0 to 2.5, and more preferably within a range of 1.0 to 2.0. Note that, by changing the rotation speed of the main shaft, the rotation speed was changed by using JIS K7117-1: the viscosity was measured at 25 ℃ with a rotational viscometer described in 1999, and the thixotropic ratio was determined by the following equation.

Thixotropic ratio (viscosity at 1rpm [ Pa s ]/viscosity at 10rpm [ Pa s ])

[ (e) organic solvent ]

In order to improve the processability of the maleimide resin composition for molding a maleimide resin film, (e) an organic solvent is added to the maleimide resin composition.

The organic solvent is not particularly limited as long as it can dissolve and uniformly disperse the maleimide resin composition. Specific examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, anisole, diphenyl ether, propyl acetate, and butyl acetate, and among these, xylene, cyclohexanone, cyclopentanone, anisole, and butyl acetate are preferably used.

When the maleimide-based resin composition comprising the components (a) to (d) as resin film components is diluted, the amount of the component (e) is optimized so that the thixotropic ratio of the diluted composition is in the range of 1.0 to 3.0, and is preferably 2 to 40 parts by mass, more preferably 3 to 30 parts by mass, based on 100 parts by mass of the total amount of the components (a) to (d).

In addition, a resin film having releasability to the maleimide resin film of the present invention may be provided on the maleimide resin film. The resin film having releasability is optimized according to the kind of the insulating resin, and specific examples thereof include a PET (polyethylene terephthalate) film coated with a fluororesin, a PET film coated with a silicone resin, a fluorine-based resin film such as PTFE (polytetrafluoroethylene), ETFE (poly (ethylene-tetrafluoroethylene)), CTFE (polychlorotrifluoroethylene), and the like. With this resin film, handling of the maleimide resin film is easy and adhesion of foreign matter such as dust can be prevented.

The thickness of the maleimide resin film of the present invention is preferably 1 to 2000. mu.m, more preferably 1 to 500. mu.m, and still more preferably 10 to 300. mu.m. When the thickness of the maleimide resin film is thinner than 1 μm, it is difficult to attach the maleimide resin film to a substrate or the like, and when the thickness of the maleimide resin film is thicker than 2000 μm, it is difficult to maintain flexibility as a film. The thickness of the film is preferably 2 times or more the particle diameter of the inorganic particles of the component (c), more preferably 3 times or more the particle diameter of the inorganic particles of the component (c), and still more preferably 5 times or more and 1000 times or less the particle diameter of the inorganic particles of the component (c). When the thickness of the maleimide resin film is within this range, the inorganic particles are less likely to form irregularities on the film, and are therefore preferred.

The method of using the maleimide resin film of the present invention includes a method of peeling a resin film having releasability from a substrate or the like, sandwiching the maleimide resin film between the substrate or the like and a semiconductor or the like, and curing the resin film by hot pressing. The temperature at the time of heating is preferably from 10 minutes to 4 hours at 100 to 300 ℃, more preferably from 20 minutes to 3 hours at 120 to 250 ℃, and still more preferably from 30 minutes to 2 hours at 150 to 200 ℃. The pressure at the time of pressure bonding is preferably 0.01MPa to 100MPa, more preferably 0.05MPa to 80MPa, and still more preferably 0.1MPa to 50 MPa.

Examples

The present invention will be described in more detail below by way of synthesis examples, and comparative examples, but the present invention is not limited to the following examples.

Maleimide (a-1)

Maleimide compound represented by the following general formula (BMI-3000 manufactured by Designer Molecules Inc.) (molecular weight 4000)

Maleimide (a-2)

Maleimide Compound represented by the following general formula (BMI-2500, manufactured by Designer Molecules Inc.) (molecular weight 3500)

Maleimide (a-3)

Maleimide compound represented by the following general formula (BMI-1500, manufactured by Designer Molecules Inc.) (molecular weight 2100)

Maleimide (a-4)

252g (1.0mol) of Kayahard AA (manufactured by Nippon chemical Co., Ltd.) and 207g (0.9mol) of pyromellitic anhydride were added to 350g of N-methylpyrrolidone, and the mixture was stirred at room temperature for 3 hours and then at 120 ℃ for 3 hours. To the resulting solution were added 196g (2.0mol) of maleic anhydride, 82g (1.0mol) of sodium acetate and 204g (2.0mol) of acetic anhydride, and the mixture was stirred at 80 ℃ for 1 hour. Thereafter, 500g of toluene was added to the reaction solution, which was further washed with water and dehydrated, and then the solvent was distilled off under reduced pressure, thereby obtaining bismaleimide (a-4) (molecular weight 1800) represented by the following general formula.

Maleimide (a-5)

Bismaleimide Compound represented by the following general formula (BMI-2300, manufactured by Dahe Kangsha Co., Ltd.) (molecular weight 400)

(a-6) epoxy resin "jER-828 EL" (manufactured by Mitsubishi chemical Co., Ltd.)

(a-7) Silicone resin "LPS-3412" (manufactured by shin-Etsu chemical industries, Ltd.)

(b-1) acrylate represented by the following general formula (KAYARAD R-684, manufactured by Nippon Kagaku Co., Ltd.)

(b-2) cyclohexyl methacrylate (light ester (LIGHT ESTER) CH (Kyoeisha chemical Co., Ltd.))

(b-3) isobornyl acrylate (manufactured by Osaka organic chemical industry Co., Ltd.)

(b-4) t-butyl acrylate (manufactured by Osaka organic chemical industries, Ltd.)

(c-1) alumina (alumina) "AC-9204" (manufactured by Admatechs, Inc., average particle diameter 10 μm, density 3.9g/cm³)

(c-2) alumina) "AO-502" (manufactured by Admatechs, Inc., average particle diameter 0.7 μm, density 3.9g/cm³)

(c-3) boron nitride "SGPS" (manufactured by Denka Co., Ltd., average particle diameter 12 μm, density 2.3 g/cm)³)

(c-4) Ag "Ag-HWQ" (manufactured by Futian Metal foil powder industries, Ltd., average particle diameter of 5 μm, density of 10g/cm³)

(c-5) yellow phosphor YAG (manufactured by Mitsubishi chemical Co., Ltd., average particle diameter 2 μm, density 3.9 g/cm)³)

(c-6) Fe-Cr-Al alloy (made by Shanyang Special Steel works Ltd., average particle diameter 4 μm, density 7.9 g/cm)³)

(c-7)Ba₂Co₂Fe₁₂O₂₂Ferrite (manufactured by shin-Etsu chemical industries, Ltd., average particle diameter of 6 μm, density of 4.1 g/cm)³)

(c-8) titanium oxide "CR-90" (manufactured by SHIYAROWAY PRODUCTS CO., LTD., average particle diameter 0.25 μm, density 4.2 g/cm)³)

(c-9) hollow silica "Silian" (manufactured by Nissan iron mine Co., Ltd., average particle diameter of 0.1 μm, density of 0.05 g/cm)³)

(D-1) dicumyl peroxide "Park Mill D" (manufactured by Nichigan oil Co., Ltd.)

(d-2) triphenylphosphine (manufactured by Tahita chemical Co., Ltd.)

[ example 1]

80g of maleimide (a-1), 19g of (b-1), 1g of (d-1) and 200g of xylene were mixed and dissolved, and 1000g of (c-3) was further added, then, the mixture was stirred in a blender, THINKY bonding MIXER (manufactured by Shinky corporation) for 3 minutes to defoam, thus, a maleimide resin composition was prepared, which was coated on an ETFE (ethylene-tetrafluoroethylene) film using an automatic coating apparatus PI-1210 (manufactured by Tester industries, Ltd.), thereby molding a film having a length of 150mm x a width of 150mm x a thickness of 50 μm, then, xylene was volatilized by heating at 100 ℃ for 30 minutes, and a solid film of 150mm in length × 150mm in width × 60 μm in thickness was prepared at 25 ℃.

Examples 2 to 9 and comparative examples 1 to 18

In examples 2 to 9 and comparative examples 1 to 16, maleimide resin compositions were prepared in the same manner as in example 1 with the compositions shown in table 1, and films were prepared with the film thicknesses shown in table 1. In comparative example 17, an epoxy resin composition was prepared using (a-6). In comparative example 18, a silicone resin composition was prepared using (a-7). In addition, a curing catalyst is already contained in (a-7). In comparative examples 16, 17 and 18, since the compatibility between the resin and the inorganic particles was poor, the thixotropy of the composition was increased, resulting in failure to form a film. Therefore, the films of comparative examples 16, 17 and 18 were not evaluated as follows.

[ thixotropic ratio before coating ]

The thixotropic ratios of the compositions were measured for examples 1 to 9 and comparative examples 1 to 18. The measurement was carried out by changing the rotation speed of the spindle and using JIS K7117-1: the viscosity at 25 ℃ was measured with a rotational viscometer described in 1999, and the thixotropic ratio was calculated by the following equation. The results are shown in tables 1-1 and 1-2.

Thixotropic ratio (viscosity [ Pa.s ] at 1 rpm/viscosity [ Pa.s ] at 10 rpm)

[ measurement of relative dielectric constant and dielectric loss tangent ]

The uncured films obtained in examples 1 to 9 and comparative examples 1 to 15 were respectively sandwiched using a mold frame of 60mm × 60mm × 0.1mm in thickness and hot-pressed at 180 ℃ for 1 hour, thereby preparing a sample. A network analyzer (Keysight Technologies, Inc. manufactured by E5063-2D5) was connected to a strand (manufactured by Keycom corporation), and the relative dielectric constant and the dielectric loss tangent of the cured product thus prepared were measured. The results are set forth in tables 2 to 7.

[ measurement of adhesive Strength ]

The films prepared in examples 1 to 9 and comparative examples 1 to 15 were attached to a silicon wafer of 20mm × 20mm, and the silicon wafer cut into 20mm × 20mm was pressed from above, and they were thermally cured (180 ℃ × 1 hour). Then, the adhesion force when the wafer was torn off from the side thereof was measured using an adhesion force measuring apparatus (Universal Bond Tester Series 4000(DS-100) manufactured by nordson advanced Technology co., Ltd). The results are shown in tables 2 to 7.

[ Density measurement ]

The uncured films obtained in examples 1 to 9 and comparative examples 1 to 15 were folded and pressed, and cured by heating at 180 ℃ for 1 hour, thereby preparing a disc-shaped cured product having a diameter of 50mm × a thickness of 3 mm. The disk-shaped cured product was used as a test piece, and the cured product was measured according to JIS K7112: 1999 Standard, the density at 23 ℃ was measured using AD-1653 (manufactured by A & D Co., Ltd.). The results are shown in tables 2 to 7.

[ measurement of thermal conductivity ]

In examples 1 to 4 and comparative examples 1 to 5 using (c-1) to (c-4) as the component (c), the obtained uncured film was folded and pressed, and cured by heating at 180 ℃ for 1 hour, and then punched into a disk shape having a diameter of 1cm and a thickness of 2mm, and the whole was coated with carbon black. The disk-shaped cured film coated with carbon black was used as a test piece, and the film was measured according to JIS R1611: 2010 standard, thermal conductivity was measured by a laser flash method (LFA 447Nanoflash netchleidevau). The results are shown in table 2 below.

TABLE 2

[ measurement of luminance ]

The uncured films obtained in example 5, comparative example 6 and comparative example 7 using (c-5) as the component (c) were sandwiched between 2 ETFE films, and compression-molded for 5 minutes at 80 ℃ and 5t using a hot press, to obtain a sheet-shaped composition sheet having a thickness of 50 μm. The obtained composition sheet was cut into a wafer size together with the ETFE film, and the composition sheet was cut into small pieces. The ETFE film on one side of the obtained sheet was peeled off, and after placing the exposed composition side on a GaN flip chip type LED wafer so as to be in contact with the LED wafer, the other ETFE film was removed. Next, the mixture was heat-molded at 180 ℃ for 30 minutes, thereby forming a phosphor-containing resin layer cured on the LED chip. The flip chip type LED device thus obtained was energized with 100mA to make the LED emit light, and the luminance was measured by an LED optical property monitor (LE-3400) manufactured by Otsuka electronics Co., Ltd. The measurements were performed on three LED devices and the average was obtained. The results are shown in Table 3.

TABLE 3

[ measurement of coercive force ]

The uncured films obtained in example 6, comparative example 8 and comparative example 9 using (c-6) as the component (c) were folded and pressed, and cured by heating at 180 ℃ for 1 hour, thereby preparing a composition sheet having a length of 3cm × a width of 4cm × a thickness of 1 mm. The coercive force of the obtained composition sheet was measured using a vibration sample magnetometer (VSM-C7, manufactured by east english industries, ltd.). The results are shown in Table 4.

TABLE 4

[ evaluation of electromagnetic wave absorption Properties ]

The uncured films obtained in example 7, comparative example 10 and comparative example 11 using (c-7) as the component (c) were folded and pressed, and cured by heating at 180 ℃ for 1 hour, thereby preparing a composition sheet having a length of 3cm by a width of 4cm by a thickness of 100 μm. An absorbance at a frequency of 37GHz was calculated using a network analyzer (8722D, manufactured by Agilent Technology co., ltd.) as an emitter and a detector, and using an antenna (CC28S, manufactured by Keycom co., ltd.), a lens (LAS-140B, manufactured by Keycom co., ltd.). The results are shown in Table 5.

TABLE 5

[ measurement of light reflectance ]

The uncured films obtained in example 8, comparative example 12 and comparative example 13 using (c-8) as the component (c) were folded and pressed, and cured by heating at 180 ℃ for 1 hour, thereby producing a disc-shaped cured product having a diameter of 50mm × a thickness of 3 mm. The light reflectance at 450nm was measured using X-rite 8200(SDG co., ltd. The results are shown in Table 6.

TABLE 6

The evaluation results of the membranes of example 9, comparative example 14 and comparative example 15 containing (c-9) hollow silica as component (c) are shown in table 7.

TABLE 7

In examples 1 to 4, a maleimide resin film having high thermal conductivity and sufficient adhesive strength was produced. In examples 5 to 9, the maleimide resin films having a high inorganic particle content and a sufficient adhesive strength were able to be produced.

In comparative example 1, the amount of the inorganic particles was insufficient, and the thermal conductivity was low. In comparative example 2, the amount of the inorganic particles was too large, so that the prepared film was brittle and the adhesive force was low. In comparative example 3, since the (meth) acrylate having 10 or more carbon atoms as the component (b) was not contained, the adhesive strength was low. In comparative examples 4 and 5, the (meth) acrylate as the component (b) had a carbon number of 7, and the adhesive strength was low. In comparative example 6, the luminance was low because the amount of the phosphor particles was insufficient. In comparative example 7, the amount of phosphor particles was too large, so that the prepared film was brittle and the adhesive strength was low. In comparative example 8, the coercive force thereof was low because the amount of the magnetic particles was insufficient. In comparative example 9, the amount of the magnetic particles was too large, so that the prepared film was brittle and the adhesion was low. In comparative example 10, the absorption rate was low because the amount of the electromagnetic wave absorbing particles was insufficient. In comparative example 11, the amount of the electromagnetic wave absorbing particles was too large, so that the prepared film was brittle and the adhesive force was low. In comparative example 12, the reflectance was low because the amount of white particles was insufficient. In comparative example 13, the amount of white particles was too large, so that the film produced was brittle and the adhesion was low. In comparative example 14, the amount of the hollow particles was insufficient, and the relative dielectric constant and the dielectric loss tangent were high. In comparative example 15, the amount of the hollow particles was too large, so that the prepared film was brittle and the adhesive force was low. In comparative examples 16, 17 and 18, the thixotropic ratio was increased due to poor compatibility between the resin and the inorganic particles, and the coating could not be applied in a film form.

As described above, the maleimide resin film of the present invention can highly fill inorganic particles with a specific composition, has various functionalities corresponding to the characteristics of the inorganic particles, and has excellent adhesion.

The present invention is not limited to the above embodiments. The above-described embodiments are illustrative, and any embodiment having substantially the same configuration as the technical idea described in the scope of claims of the present invention and exhibiting the same operational effects is also included in the technical scope of the present invention.

Claims

1. A maleimide resin film comprising:

(a) a maleimide represented by the following formula (1),

in the formula (1), A independently represents a tetravalent organic group containing a cyclic structure, B independently represents an alkylene group having at least one aliphatic ring having at least 5 carbon atoms and having at least 6 carbon atoms and optionally containing a heteroatom, Q independently represents an arylene group having at least 6 carbon atoms and optionally containing a heteroatom, W represents a group represented by B or Q, n is 0 to 100, m represents a number of 0 to 100, wherein at least one of n and m is a positive number;

(b) a (meth) acrylate having 10 or more carbon atoms;

(c) inorganic particles; and

(d) a curing catalyst is used for curing the epoxy resin,

2. The maleimide resin film according to claim 1,

the organic group represented by A in the formula (1) is any of tetravalent organic groups represented by the following structural formula,

the bonding position of the unbonded substituent in the above structural formula is bonded to the carbonyl carbon forming the cyclic imide structure in formula (1).

3. The maleimide resin film according to claim 1,

4. The maleimide resin film according to claim 1,

5. The maleimide resin film according to claim 1,

6. The maleimide resin film according to claim 1,

7. The maleimide resin film according to claim 1,

(c) the inorganic particles of the component (A) are selected from iron, cobalt, nickel, stainless steel, Fe-Cr-Al-Si alloy, Fe-Si-Al alloy, Fe-Ni alloy, Fe-Cu-Si alloy, Fe-Si-B (-Cu-Nb) alloy, Fe-Si-Cr-Ni alloy, Fe-Si-Cr alloy, Fe-Si-Al-Ni-Cr alloy, Fe-Cr-Al-Ni-Cr alloy, Fe-Cr-Al-Cr-Fe-Cr alloy, and Fe₂O₃、Fe₃O₄Mn-Zn-based ferrite, Ni-Zn-based ferrite, Mg-Mn-based ferrite, Zr-Mn-based ferrite, Ti-MnAt least one magnetic particle selected from ferrite-like particles, Mn-Zn-Cu-like particles, barium ferrite particles and strontium ferrite particles.

8. The maleimide resin film according to claim 1,

9. The maleimide resin film according to claim 1,

10. The maleimide resin film according to claim 1,

11. A composition for a maleimide resin film, which is a maleimide resin composition constituting the maleimide resin film according to claim 1,